The reaction of molybdenum hexacarbonyl with C6H5CH2OC6H4ONa and Et4NBr in CH3CN at 60 ℃ afforded the di-nuclear Mo（0） compound [Et4N]3[Mo2（CO）6（μ-OC6H4OCH2C6H5）3] 1. 1 crystallizes in monoclinic, space group ...The reaction of molybdenum hexacarbonyl with C6H5CH2OC6H4ONa and Et4NBr in CH3CN at 60 ℃ afforded the di-nuclear Mo（0） compound [Et4N]3[Mo2（CO）6（μ-OC6H4OCH2C6H5）3] 1. 1 crystallizes in monoclinic, space group P21/c with a = 15.359（2）, b = 18.378（3）, c = 24.952（2） A, β = 102.268（4）°, V = 6882.3（1 6） A^3, Mr = 1348.34, Z = 4, Dc = 1.301 g/cm^3, F（000） = 2832 and μ= 0.424 mm^-1 The final R = 0.0606 and wR = 0.1552 for 9396 observed reflections （I 〉 2σ（I））. I contains a [Mo2O3]^3 core in triangular bi-pyralnidal configuration and each Mo atom adopts a distorted octahedral geometry with three carbon atoms from carbonyls and three ,μ-O atoms from C6H5CH2OC6H4O^- bridging ligands. The Mo…Mo distance is 3.30（8） A, indicating no metalmetal bonding. A formation pathway via forming a di-molybdenum（0） di-bridging OR compound [Mo2（μ-OR）2（CO）8]2 has been figured out and the reaction of Mo（CO）6 with alkoxide has also been discussed.展开更多
The Huoshenmiao δeposit is Mo skarn δeposit, located in the western part of the Luanchuan ore δistrict.Mineralization process can be δivided into a skarn and a quartz-sulfide episodes with six stages: prograde(I),...The Huoshenmiao δeposit is Mo skarn δeposit, located in the western part of the Luanchuan ore δistrict.Mineralization process can be δivided into a skarn and a quartz-sulfide episodes with six stages: prograde(I), retrograde(II), quartz-K-feldspar(III), quartz-molybdenite(IV), quartz-pyrite(V), and quartzcalcite(VI). A combined study of geochronology, fluid inclusion(FI), and stable isotopes was conducted to constrain the mineralization age, source of ore materials, as well as the origin and evolution of the ore-forming fluids. Molybdenite Ree Os δating indicates that the δeposit was formed in the Late Jurassic(~145 Ma). The δ^(34)S values of sulfides range from 3.0‰ to 7.1‰, implying that the ore materials in the δeposit are magmatic in origin. Three types and six subtypes of FIs are δistinguished, namely, aqueous two-phase(W_1-and W_2-type), δaughter mineral-bearing multiphase(S_1-and S_2-type), and CO_2-bearing three-phase(C_1-and C_2-type). In stages I and II, the W_1-type FIs δisplay homogenization temperatures(Th) from 496°C to >600°C, with salinities of 14.9-18.3 wt.% NaCl eqv. The FIs in stages III, IV and early stage V composed of coeval S-, C-and W-types, respectively homogenize at similar Th, suggesting the occurrence of boiling. The W1-type FIs in late stage V and stage VI, yield Th of 102-406°C and salinities of 0-4.7 wt.% NaCl eqv. The δD_(H_2O)and δ^(18) O(H_2O)values of the ore-forming fluids in quartz-sulfide episode vary from-112‰ to-76‰, and 11.0‰ to 1.0‰, respectively. All these above observations reveal that the early ore-forming fluids are magmatic in origin, and characterized by high temperature and moderate to high salinity, and gradually evolve to low temperature, low salinity meteoric water. The Huoshenmiao Mo δeposit is associated with the magmatism event induced by the protracted subduction of the Izanagi plate beneath the eastern China continent. The δecrease in temperature, salinity and f(O_2), as well as change of p H δue to boiling and fluid-rock interaction, are the main factors controlling Mo δeposition.展开更多
基金This research was supported by NNSFC (No. 90203017 29733090), NBRP (2004CB7201005) and SKLSC
文摘The reaction of molybdenum hexacarbonyl with C6H5CH2OC6H4ONa and Et4NBr in CH3CN at 60 ℃ afforded the di-nuclear Mo（0） compound [Et4N]3[Mo2（CO）6（μ-OC6H4OCH2C6H5）3] 1. 1 crystallizes in monoclinic, space group P21/c with a = 15.359（2）, b = 18.378（3）, c = 24.952（2） A, β = 102.268（4）°, V = 6882.3（1 6） A^3, Mr = 1348.34, Z = 4, Dc = 1.301 g/cm^3, F（000） = 2832 and μ= 0.424 mm^-1 The final R = 0.0606 and wR = 0.1552 for 9396 observed reflections （I 〉 2σ（I））. I contains a [Mo2O3]^3 core in triangular bi-pyralnidal configuration and each Mo atom adopts a distorted octahedral geometry with three carbon atoms from carbonyls and three ,μ-O atoms from C6H5CH2OC6H4O^- bridging ligands. The Mo…Mo distance is 3.30（8） A, indicating no metalmetal bonding. A formation pathway via forming a di-molybdenum（0） di-bridging OR compound [Mo2（μ-OR）2（CO）8]2 has been figured out and the reaction of Mo（CO）6 with alkoxide has also been discussed.
基金funded by the National Key R&D Plan (Nos. 2017YFC0601403 and 2016YFC0600106)the National Natural Science Foundation of China (No. 41272110)the basic research program of the First Institute of Oceanography (No. 2015T02)
文摘The Huoshenmiao δeposit is Mo skarn δeposit, located in the western part of the Luanchuan ore δistrict.Mineralization process can be δivided into a skarn and a quartz-sulfide episodes with six stages: prograde(I), retrograde(II), quartz-K-feldspar(III), quartz-molybdenite(IV), quartz-pyrite(V), and quartzcalcite(VI). A combined study of geochronology, fluid inclusion(FI), and stable isotopes was conducted to constrain the mineralization age, source of ore materials, as well as the origin and evolution of the ore-forming fluids. Molybdenite Ree Os δating indicates that the δeposit was formed in the Late Jurassic(~145 Ma). The δ^(34)S values of sulfides range from 3.0‰ to 7.1‰, implying that the ore materials in the δeposit are magmatic in origin. Three types and six subtypes of FIs are δistinguished, namely, aqueous two-phase(W_1-and W_2-type), δaughter mineral-bearing multiphase(S_1-and S_2-type), and CO_2-bearing three-phase(C_1-and C_2-type). In stages I and II, the W_1-type FIs δisplay homogenization temperatures(Th) from 496°C to >600°C, with salinities of 14.9-18.3 wt.% NaCl eqv. The FIs in stages III, IV and early stage V composed of coeval S-, C-and W-types, respectively homogenize at similar Th, suggesting the occurrence of boiling. The W1-type FIs in late stage V and stage VI, yield Th of 102-406°C and salinities of 0-4.7 wt.% NaCl eqv. The δD_(H_2O)and δ^(18) O(H_2O)values of the ore-forming fluids in quartz-sulfide episode vary from-112‰ to-76‰, and 11.0‰ to 1.0‰, respectively. All these above observations reveal that the early ore-forming fluids are magmatic in origin, and characterized by high temperature and moderate to high salinity, and gradually evolve to low temperature, low salinity meteoric water. The Huoshenmiao Mo δeposit is associated with the magmatism event induced by the protracted subduction of the Izanagi plate beneath the eastern China continent. The δecrease in temperature, salinity and f(O_2), as well as change of p H δue to boiling and fluid-rock interaction, are the main factors controlling Mo δeposition.
